Cement and Concrete Research 39 (2009) 433439

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Cement and Concrete Research

j o u r n a l h o m e p a g e : h t t p : / / e e s . e l s e v i e r. c o m / C E M C O N / d e f a u l t . a s p

Early hydration and setting of Portland cement monitored by IR,

SEM and Vicat techniques
Rikard Ylmn, Ulf Jglid, Britt-Marie Steenari, Itai Panas
Department of Chemistry and Biotechnology, Environmental Inorganic Chemistry, Chalmers University of Technology, S-41296 Gothenburg, Sweden

a r t i c l e i n f o a b s t r a c t

Article history: Diffuse Reectance Infrared DR-FTIR spectroscopy is employed to monitor chemical transformations in pastes
Received 26 November 2007 of Portland limestone cement. To obtain a sufcient time resolution a freeze-dry procedure is used to
Accepted 30 January 2009 instantaneously ceasing the hydration process. Rapid re-crystallization of sulphates is observed during the
rst 15 s, and appears to be complete after ~ 30 min. After ~ 60 min, spectroscopic signatures of polymerizing
Keywords: silica start to emerge. A hump at 9701100 cm 1 in conjunction with increasing intensity in the water
Hydration
bending mode region at 15001700 cm 1 is indicative of the formation of Calcium Silicate Hydrate, C-S-H.
Calcium-silicate-hydrate (C-S-H)
Spectroscopy
Simultaneously with the development of the C-S-H signatures, a dip feature develops at 800970 cm 1,
Cement paste reecting the dissolution of Alite, C3S. Setting times, 180 (initial) and 240 (nal) minutes, are determined by
Portland cement the Vicat technique. Combining DR-FTIR, SEM and Vicat measurements it is concluded that the setting is
caused by inter-particle coalescence of C-S-H.
2009 Elsevier Ltd. All rights reserved.

1. Introduction obtain chemical information. Morphological information may be

Today, Portland cement is a widely used binder in concrete
construction. C3S (alite) and C2S (belite) is essential to the build-up of
strength in Portland cement. These two calcium-silicate phases are
formed above 800 C, where C3S is preferentially formed upon
elevating the temperature and increasing amount of added burned
lime, CaO. C3S is responsible for short term strength development
(days to months) while C2S displays the better long term strength
development performances (~ years). The quest for increasingly
shorter setting time and early strength has seen the C3S/C2S ratio
increase in commercial Portland cement. In recent years, the increased
attention on environmental aspects of material conversion has
inuenced research towards possible modications of Portland
cement to better meet the increasing demands for sustainability in
the construction sector. This is done by using additives and changing
the composition of the cement. Many different experimental
techniques have been employed to investigate the effects on material
conversion as Portland cement is dissolved and transformed into
calcium-silicate-hydrate, C-S-H. For determination of setting times,
Vicat measurements are often employed. At later stages in the
hydration process, an ultrasonic cement analyser may be used to
determine changes in the elastic modulus of the mortar [1,2].
Calorimetry is employed to monitor the heat released upon hydration
[37], whereas X-ray diffraction [813], nuclear magnetic resonance
[1416] and Fourier transform infrared spectroscopy, FTIR, are used to
Corresponding author. Tel.: +46 31 7722860; fax: +46 31 7722853.
E-mail address: itai@chalmers.se (I. Panas).
obtained by means of scanning electron microscopy and transmission
electron microscopy [11,12,15,17].
Spectroscopic methods are commonly used to study the chemistry of
cement hydration. In the present work the hydration of Portland cement
has been monitored mainly by means of infrared spectroscopy. In
infrared spectroscopy one utilizes that molecules or groups of atoms on
large molecules absorbs different wavelengths of infrared light depend-
ing on which atoms that constitute the molecule or group, its geometry
and its immediate surroundings. It can therefore be used to study both
crystalline and amorphous samples. The sample is irradiated with
infrared light with a span of different wavelengths. The sample will
absorb some of the light at wavelengths that are characteristic to its
chemical composition. To see at which wavelengths the sample has
absorbed light the intensity at each wavelength is measured with and
without sample. IR radiation only penetrates about 1 wavelength into the
sample (~10 m for 1000 cm 1), making it ideal in the study of surface
processes.
In previous studies where FTIR was used to study the hydration of
cement and its components, the sample was prepared by mixing the
cement with KBr and pressing the mixture into pellets [1821]. The
usefulness of Diffuse Reectance Fourier Transform Infrared Spectro-
scopy, DR-FTIR, as a tool for studying the hydration of cement has also
been demonstrated in previous work [22,23]. A comparison between DR-
FTIR and the KBr pellet technique has been done by Delgado et al. [24],
who showed that the methods produce similar spectra. The advantage of
the KBr technique is that it provides better dened bands than DR-FTIR,
but the sample preparation is more labour intensive. The results of the
present study suggest that the DR-FTIR technique employed is indeed

0008-8846/$ see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cemconres.2009.01.017
434 R. Ylmn et al. / Cement and Concrete Research 39 (2009) 433439

preferred in that external physico-chemical interference is minimized, Table 1

Possible assignment to some of the peaks observed in Figs. 25.
i.e. the hydration products are studied in the proper cement matrix with
a minimum of sample tampering, and avoiding contact with foreign Wave number [cm 1] Possible assignment Reference
chemicals. Differential IR light absorption of samples which have been 656658 4 of SiO4 [21,40]
allowed to hydrate for different times is reported here. 714 4 of CO3 [22,32,35,37]
847848 AlO, AlOH [21,35]
Water displays strong absorption in the mid-IR range, which
877878 2 of CO3 [21,22,35,37]
makes it virtually impossible to perform in situ studies of cement 10111080 Polymerized silica [19]
hydration. A second draw back of in situ DR-FTIR for the study of ~ 11001200 3 of SO4 [19,22,31,32]
cement hydration is that the surface of the cement paste, while 12001202 Syngenite, thenardite [3234]
hydrating, may become too at for the diffuse reectance technique to 14001500 CO3 [19,21,22,35,37]
16201624 2 of water in sulphates [22,31,33]
be efciently used. These considerations validate selection of an ex
16401650 2 H2O [21,35,36]
situ DR-FTIR approach. 16821684 2 of water in sulphates [22,31,33]
To study very early hydration using an ex situ technique, it is 17951796 CaCO3 Own measurement, [22]
imperative that the hydration is stopped instantaneously at a 25132514 CaCO3 Own measurement, [22]
predetermined time. To satisfy this requirement, a freeze-dry 28752879 CaCO3 Own measurement, [22]
29832984 CaCO3 Own measurement, [22]
technique is adopted in this research. The freezing of the sample 33193327 Syngenite, thenardite [3234]
with liquid nitrogen ensures that all chemical processes are very much 33983408 3 of H2O, capillary water [36]
retarded, while the subsequent water evaporation step at low 3457 1 + 3 of H2O [21,36]
temperature minimizes any thermally induced chemical transforma- 3554 3 of H2O in gypsum [22,31]
3611 Bassanite [22]
tions other than water removal while drying. Indeed, earlier
36413644 Ca(OH)2 Own measurement, [20,23,24,37]
microscopy work [2527] has shown that freezing is a relatively
mild method to stop hydration. The drying will of course affect the
structures of some phases. Bound water, like in ettringite, could be
partially removed, and morphological properties may change upon
removal of water. between 400 and 4000 cm 1. The diffuse reectance technique is
The purpose of the present study is to demonstrate the efciency utilized, in which the incident beam is allowed to be reected off the
of the freeze-dry procedure in conjunction with DR-FTIR spectroscopy ground sample towards an overhead mirror upon which the diffusely
for studying the complex hydration chemistry of Portland cement. An scattered rays are collected and measured in the detector. A more
attempt to correlate relevant spectroscopic signatures to the devel- detailed description is given by Fuller and Grifths [28]. The sample is
opment of strength in the system is also made. Strength development scanned 64 times with a resolution of 2.0 cm 1 and the presented
is monitored here by means of Vicat measurements. data is an average value. Each sample was prepared and analyzed 3
times and the nal spectrum was an average of these 3 measurements
2. Experimental to minimize differences due to sample preparation.
The batch size was 200 g of as received dry cement. As the cement
The Portland cement used was a Portland limestone cement, hydration was studied from 15 s the cement paste was only mixed for
byggcement Std PK Skvde CEM II/A-LL 42,5 R, from Cementa AB. 15 s. However, the chemical development of the cement paste was
An automatic/manual mortar mixer 39-0031 from ELE International found to be insensitive of mixing time as long as the cement was
was used. The cement was mixed with distilled deionized water that completely wetted [29]. Samples were prepared in plastic dishes of
was poured into the mixing bowl before adding the cement. The ratio 35 mm in diameter. The thickness of the paste in the dishes was ~2
of water to as received dry cement was 0.4 by weight in both DR-FTIR 3 mm. Lids were placed over the dishes while they hydrated to
and Vicat measurements. The cement was carefully added and the prevent water from evaporating. The samples were hydrated between
paste was mixed at 140 rpm on the mixing blade and 62 rpm on the 15 s and 360 min in normal laboratory environment, then frozen by
mixing head. The hydration time was measured from the instant when immersion in liquid nitrogen and subsequently placed in the freeze
the cement was added to the water. drier overnight. Measurements were made the following day. Before
measurement the sample was ground and placed in the sample holder
2.1. DR-FTIR of the DR-FTIR spectrometer. To obtain good reproducibility, great care
was taken when grinding the samples and placing them in the sample
The spectrometer used was a Nicolet Magna-IR 560 with an insert cup to make the samples as similar as possible.
cell for diffuse reectance spectroscopy. The measurement range lies
2.2. Vicat

The batch size was 300 g of as received dry cement and the cement
paste was mixed for 2 90 s with a stop in between for 15 s to scrape
the paste from the inside walls. The Vicat apparatus used was a
Vicatronic automatic recording apparatus E040 and measurements
were performed in a 40 mm mould with a calibrated weight of 300 g
and a cylindrical needle with at tip area of 1 mm2.

2.3. Scanning electron microscopy

Fig. 1. Vicat measurement showing the depth of penetration of the Vicat needle into the
cement as function of time. The height of the mould was 40 mm.
The microscope used was a FEI Quanta 200 FEG ESEM operated in
secondary electron detection mode with high-vacuum and an
acceleration voltage of 2 kV. Some of the freeze-dried samples were
pulverized. Since the freeze-dried samples were barely holding
together this was easily done with a metal spoon. Some of the
powder was placed on carbon tape attached to the sample holder.
 R. Ylmn et al. / Cement and Concrete Research 39 (2009) 433439
Several regions were examined to make sure that the observed
structures were representative of the sample.
3. Results
The present study attempts to correlate setting with the evolution
of spectral features in DR-FTIR spectra during early hydration of
cement. The Vicat setting time measurement for the used Portland
cement is displayed in Fig. 1. Initial and nal set are seen to occur at
180 min and 240 min respectively. In Section 3.1, the overall time
evolution of DR-FTIR absorption intensities is presented. Possible
assignments of the different bands are shown in Table 1, and
interpreted in Sections 3.1.23.1.4.
3.1. Time resolved spectra of hydrating cement
The hydration process was monitored for the rst six hours by
applying the freeze dry method, grinding of sample and subsequently
acquiring the DR-FTIR spectra. The recorded absolute spectra of dry
and hydrated cement are displayed in Fig. 2. It shows the spectra of the
as received dry cement together with the cement just after it has been
mixed (15 s), after 180 min and 360 min of hydration. Weak signatures
of hydration can be seen in the 9001200 cm 1 region. To enhance
these effects, various difference spectra were constructed. In Fig. 3, the
difference spectra employ as received dry cement as reference. Now,
the spectroscopic features can be seen signicantly clearer and we
observe the development and saturation band at 11001200 cm 1
already after 15 s. This is complemented by a more slowly growing
feature at 9001100 cm 1. Because the bands that developed after
15 s cannot be associated with the actual hardening of cement paste,
the 15 s spectrum was taken as reference in Figs. 4 and 5. Fig. 3
supports the overall procedure in that a smooth background is
observed in the relevant spectral regions. Having found this, Fig. 5
focuses on the 5002000 cm 1 interval and the spectra for twelve
different hydration times are displayed.
3.1.1. Sulphate bands
The sulphates originally present in Portland cement are gypsum
(CaSO42H2O), hemihydrate (bassanite, CaSO40.5H2O) and anhy-
drite (CaSO4). The latter ones are formed when the gypsum is ground
with the cement clinker. The heat makes some of the crystal water in
the gypsum to dissociate. When water is added to the cement the
sulphates react with the aluminate and ferrite phases of the cement to
produce AFt phase. This phase in turn reacts further with the
aluminate and ferrite phases to form the AFm phase [30].
Fig. 2. Absorbance of as received dry cement and cement that has been allowed to
hydrate for 15 s, 180 min and 360 min after the cement was added to the water. The
spectra are shown offset for clarity.
435
Fig. 3. Difference spectra where the absorbance spectrum of as received dry cement has
been subtracted from the absorbance spectra of cement hydrated for 15 s, 180 min and
360 min. The spectra are shown offset for clarity.
Characteristic sulphate absorption bands are generally found in the
range 11001200 cm 1 due to the 3 vibration of the SO2 4 -group in
sulphates [19,22,31,32]. It is very difcult to interpret this area by
studying FTIR-spectra only, since the many forms of sulphates give rise
to several peaks here and cause lots of overlaps, but also because the
3 vibration of the SiO2
4 -group can absorb in this region, especially
when it has polymerized [21]. Therefore no in-depth analysis of it will
be done in this work. In the DR-FTIR spectrum of as received dry
cement (Fig. 2, bottom spectrum), a broad feature is seen in 1100
1200 cm 1 region reecting mainly amorphous sulphates. Immedi-
ately after mixing with water, some sharp absorption bands develop at
1100 cm 1, 1200 cm 1 and 3320 cm 1, indicative of very rapid
dissolution of sulphates followed by crystallization (Fig. 2, 15 s
spectrum). This can also be inferred by considering the 15 s difference
spectrum in Fig. 3. This spectrum corresponds to the difference
between that acquired after 15 s of hydration, and the spectrum of dry
cement. Spectral signatures of sulphate chemistry after 15 s of
hydration, corresponding to re-crystallization are obtained. Appar-
ently, crystalline sulphate phases form very early in the hydration
process, after which they become inactive spectator phases. The
extent to which this holds true can be assessed by replacing the as
received dry cement reference spectrum for that of 15 s hydrated
cement (Figs. 4 and 5). From Fig. 5 we observe signicant changes in
the sulphate absorption bands up to 30 min of hydration. Apparently,
intermediate phases are formed consistent with the absorption
Fig. 4. Difference spectra in the range 4004000 cm 1 where the absorbance spectrum
of the freshly mixed cement (15 s) has been subtracted from the absorbance spectra of
cement hydrated for 30 s, 5 min, 120 min and 360 min. The spectra are shown offset for
clarity.
436 R. Ylmn et al. / Cement and Concrete Research 39 (2009) 433439

spectra of syngenite (K2Ca(SO4)2H2O) and thenardite (Na2SO4) or

closely related compounds [3234]. At any rate, after 60 min, little
changes can be seen in the sulphate absorption region of the spectra.

3.1.2. Water associated bands

In the spectrum for as received dry cement there is a peak at
1623 cm 1 and a smaller one at 1684 cm 1. These are caused by the
bending vibration 2 of water in sulphates, mainly gypsum [22,31,33].
The peak at 3554 cm 1 is caused by the 3 vibration of water in
gypsum [22,31] and the peak at 3611 cm 1 could be caused by
bassanite (CaSO40.5H2O). As hydration progresses there is a broad
feature forming with its centre at ~ 1650 cm 1, caused by the bending
vibration 2 of irregularly bound water [21,35,36]. The consumption of
gypsum can be seen as dips in this feature at 1623 cm 1 and 1680 cm 1
(Figs. 4 and 5). A small increase in gypsum during the rst 10 min is
implied, and may be due to the transformations of anhydrite and
Fig. 6. Difference spectra in the range 5002000 cm 1 where the absorbance spectrum
bassanite. The background level for wave numbers N1600 cm 1 is of cement hydrated for 30 min has been subtracted from the absorbance spectra of
steadily increasing with increasing hydration times. Since there seems to cement with hydration times from 60360 min. The spectra are shown offset for clarity.
be no corresponding decrease in any other area, this is probably caused
by the incorporation of water. The absorption intensities due to the 2
vibration mode of water at ~1650 cm 1 and the 1 +3 modes silica [21,23,37,38] to form calcium silicate hydrate C-S-H (vide infra).
at ~3450 cm 1 and results from Mollah et al. and Yu et al. support In order to focus on the silica chemistry, the 15 s reference spectrum is
this observation [21,36]. replaced by that acquired after 30 min (see Fig. 6), i.e. after the
sulphate chemistry has stopped. Monotonous growth of the C-S-H
3.1.3. Silica associated bands associated absorption intensities (9701100 cm 1) is observed. The
After about 2 h of hydration new spectral intensity shifts are dip in the absorption spectrum at 800970 cm 1, which deepens with
observed from ~ 900 cm 1 towards ~10001100 cm 1 (see Figs. 35), time, is due to the dissolution of the C3S clinker phase [39]. The
neither associated with sulphates nor water, suggestive of rearrange- intensities in the dip (800970 cm 1) and hump (9701100 cm 1)
ments in the silica subsystem. These dip-hump features are taken to regions in Fig. 6 were integrated in an attempt to correlate the clinker
reect dissolution of alite and simultaneously the polymerization of dissolution with the silica polymerization. A horizontal line at the
intensity at 970 cm 1 was used as baseline. The result is plotted in
Fig. 7.

3.1.4. Hydroxides and carbonates

The peak at 3643 cm 1 (see Table 1 and Figs. 2 and 3) corresponds
to Ca(OH)2, which is formed as silicate phases in the cement dissolve.
The peaks at 1796 cm 1, 2513 cm 1, 2875 cm 1, 2983 cm 1 and
the shoulder at 13501550 cm 1 are due to that portion of calcium
carbonate, which is added to the cement by the manufacturer after
clinker calcination. The amount of calcium carbonate is seen to
decrease as the hydration progresses, i.e. negative absorption bands in
the difference spectra of Figs. 3 and 4. This may partly be due to the
reaction of calcite with the aluminate to form less crystalline phases
such as carboxyaluminates [40,41] or the carbonate ion can substitute
for sulphate ions in Aft and AFm phases [13,30]. The peak growing
at ~1070 cm 1 could be the 1 vibration of CO3-group in the formed
carbonates [33,35], but this observation would contradict the overall

Fig. 5. Difference spectra in the range 5002000 cm 1 where the absorbance spectrum Fig. 7. Integrated value of the absorbance in the intervals 800970 cm 1 (upper dots)
of the freshly mixed cement (15 s) has been subtracted from the absorbance spectra of and 9701100 cm 1 (lower dots) in Fig. 6 as function of hydration time of the cement.
cement with hydration times from 30 s to 360 min. The spectra are shown offset for The lines are drawn on free hand to guide the eye and does not represent a
clarity. mathematical model.
 R. Ylmn et al. / Cement and Concrete Research 39 (2009) 433439 437

Fig. 8. SEM pictures of cement at different stages of hydration. a) Surface of unhydrated particle. b) Surface of particle hydrated for 15 s. c) Surface of particle hydrated for 120 min. d)
Surface of particle hydrated for 240 min. e) Surface of particle hydrated for 480 min. f) Surface of particle hydrated for 480 min at larger magnication.
438 R. Ylmn et al. / Cement and Concrete Research 39 (2009) 433439
reduction of carbonate absorption intensities with time. A more
plausible candidate for this absorption band is the stretching vibration
of SiO, which is also found in jennite (Ca8(Si6O18H2)(OH)8Ca6H2O)
[37,38].
3.2. SEM
SEM pictures of cement grains at different stages of hydration are
displayed in Fig. 8. The surfaces of the unhydrated particles are bare,
with debris lying on top (Fig. 8a). After 15 s and 120 min of hydration
(Fig. 8b, c) the surfaces of the cement particles are still found to be
bare, but lumps and platelets have formed in addition to the debris
present already on the unhydrated particles. Fig. 8d shows cement
after 240 min of hydration. Now a carpet is covering the cement
particles. The carpet has grown even more after 480 min of hydration
and is seen to consist of needle-like protruding structures (Fig. 8e, f).
4. Discussion
A longstanding issue concerns the roles of various phases during
early hardening of Portland cement. In particular the roles of
sulphates, added to the Portland cement as anhydrous (CaSO4),
hemihydrate (CaSO40.5H2O), and gypsum (CaSO42H2O) have been
much discussed in this context. Indeed, the general consensus is that
the dissolution and re-crystallization of the various sulphate contain-
ing phases is completed well before the setting occurs [42,43]. Yet, due
to the complexity and instability of the early cement chemistry, the
sulphates, besides their well known function as water absorbents,
have been empirically found to affect the morphology of the hydrating
paste both by providing a background ionic strength and by forming
intermediate phases, which suppress ash setting. In the present
study, results show that the sulphate related DR-FTIR absorption
bands display large changes in the 11001200 cm 1 interval but that
this occurs mainly during the rst 10 min of hydration, during which
the development of sharp bands imply the formation of crystalline
phases. The appearing platelets and hexagonal crystals seen with SEM
are possibly associated with these phases. After 30 min, the inter-
conversion of sulphate phases has apparently stopped. The sulphates
formed are most probably ettringite or monosulphate, as earlier
studies on cement hydration have shown that these sulphates are
formed during the rst minutes of hydration [11,43,44]. In this study
of the evolution of the C-S-H absorption bands, the 30 min spectrum
was chosen as reference. The degree to which the sulphate chemistry
is completed at this time can be appreciated by studying 1100
1200 cm 1 region in Fig. 6, keeping in mind that C-S-H also displays
absorption bands in this interval.
By DR-FTIR spectroscopy, detectable amounts of polymerized silica
are formed after approximately 1 h of hydration, as seen in Fig. 6 in the
9001100 cm 1 interval. It is gratifying to note how well the
integrated intensities at 800970 cm 1 as function of time (Fig. 7)
correlate with the quantitative X-ray diffraction study on C3S
hydration by Taylor et al. [45], who interpreted their results to imply
C-S-H formation. The fact that the growth of the hump feature at 970
1100 cm 1 follows the C3S dissolution process implies that the
signature of polymeric silica indeed corresponds to C-S-H formation. It
can be noted how the formation of polymerized silica (9701100 cm 1)
is correlated in time with an increased incorporation of water in the
structure as seen in the absorption interval at 15001700 cm 1. This
supports further that calcium silica hydrate C-S-H is a major product
formed upon early Portland cement hydration, as C-S-H consists of
polymerized silica and calcium ions with water incorporated.
It becomes interesting to attempt to correlate the materials
conversion observed with DR-FTIR with morphological changes as
seen with SEM. The acceleration phase of C-S-H formation starts
somewhere between 120 and 180 min (Figs. 6 and 7). Simulta-
neously a growth of a needle-like phase is developed on the cement
particles (Fig. 8). This phase has been attributed to C-S-H in previous
studies of alite, C3 S, where no other phase than C-S-H and
portlandite (Ca(OH)2) is formed [25,46]. It is seen in Fig. 1 that the
setting starts after 180 min, and that it is completed after 240 min.
Since the conversion of the sulphates occurs during the rst 30 min,
the possibility that the needle-like phase is due to sulphates is ruled
out. However, the acceleration phase of C-S-H formation (vide supra)
occurs on the same time scale as the formation of the needle-like
phase seen by SEM as well as that of the setting process. An
identication of C-S-H as the phase responsible for the setting of the
Portland cement is thus arrived at. Support is produced to the claim
that C-S-H is responsible for the initial development of strength in
Portland cement pastes. Also, it is suggested that C-S-H is formed
continuously during hydration and in particular so prior to the
setting. This implies that the actual setting is due to coalescence of
clinker grains and that it is associated with the formation of
sufcient amounts of C-S-H, to increase friction and bridge the
inter-grain distances.
The present ndings are consistent with those of Chen and Odler
[43], who reach the conclusion that setting in ordinary Portland
cement is mainly due to the formation of C-S-H as long as the ratio
between sulphates and C3A + C4AF is balanced, else false setting
results due to the formation of ettringite or monosulphate.
5. Conclusions
Cement is a complex material, and its hydration possibly provides
additional complexity. Indeed, as yet no single method exists which
completely determines all chemical reactions taking place in a cement
structure from the mixing and onward. Therefore several comple-
mentary techniques must be used.
In the present study, signatures of early setting of an untampered
limestone Portland cement were extracted by correlating DR-FTIR, SEM,
and Vicat measurements. The objective of this paper was to demonstrate
how diffuse reectance Fourier transform infrared spectroscopy in
combination with freeze-drying may add a piece of the puzzle regarding
material conversion during the very early stages of cement hydration,
down to fractions of a minute. Whereas setting of each unique cement
must be addressed separately, a method to monitor the material
conversions during early hydration has been presented.
Summarizing:
the time evolution of the sulphate chemistry displays very rapid
crystallization followed by a slow recrystallization phase, which is
completed within approximately 30 min;
the appearance of a broad absorption hump at 9701100 cm 1 after
60 min of hydration is due to polymeric silica. It is correlated with the
development of water bending vibration bands (15001700 cm 1).
This implies the formation of calcium silicate hydrate, C-S-H;
time dependent changes in morphology due to the hydration
process, as monitored with SEM, were found to correlate with the
DR-FTIR signatures of C-S-H formation,
the growth of a dip feature in the spectra at 800970 cm 1, identied
as the dissolution of C3S Alite, correlates with the formation of C-S-H.
Vicat setting begins after 180 min and is completed after 240 min.
This occurs well after the sulphate reactions have stopped. However,
the C-S-H formation in the acceleration phase of C3S dissolution,
displays the same time dependence as that of the setting process. The
observations support the understanding of setting in terms of
coalescing C-S-H coated Portland cement particles.
Acknowledgements
The support from the Knowledge foundation (KK stiftelsen), the
Swedish Research Council, and Eka Chemicals Inc., Bohus is gratefully
acknowledged, as well as valuable discussions with Inger Jansson.
 R. Ylmn et al. / Cement and Concrete Research 39 (2009) 433439
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